Waterinsoluble azodyestuffs



Patented Jan. 7, 1936 UNITED STATES 2,026,908 PATENT OFFICE 2,026,908 WATERINSOLUBLE AZODYESTUFFS Friedrich Muth,

Leverkusen-I. G.-Werk, Germany, assignor to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application June 26, 1934, Serial No. 732,535. In Germany October 5, 1932 12 Claims. (Cl. 260 53) The present invention relates to waterinsoluble azodyestufis, and to fibres dyed therewith, more particularly it relates to dyestufis which may be represented by the general formula:

naphthindole-, benzothiazole-, naphthothiazole radical which may bear substituents, such as halogen, the cyano group, the nitro group, a carboxylic acid ester group, the group the acetylamino group, the methoxy-acetyl- 35 amino group, the benzoylamino group, a monoor di-alkyl-, -aralkylor -arylamino-group, methoxy, ethoxy, butoxy, benzyloxy, phenoxy, an alkylketone group, an arylketone group, the

benzoyl group, an SOz-alkyl-, -aralkylor -aryl-- group, a monoor di-alkyl-,aralkylor -arylsul-' foneamide group, methyl, ethyl, propyl, butyl, amyl, benzyl, phenyl, trifiuoromethyl, the radical of a diazo compound, such as N=NC6Hs,,

45 one of the numbers one and two. 4

My new dyestuffs of the above identified general formula are obtainable by diazotizing in the usual manner a primary amine suitable for preparing azodyestuffs free from a substituent in- 50 ducing solubility in water and coupling in substance or on a substratum, especially the vegetable fibre, with an arylamide of the general formula:

wherein a: and R mean the same as stated above. 60 The dyestuffs thus obtained generally yield brown to blackish brown to black shades, those prepared on the fibre according to one of the usual dyeing or printing processes being distinguished by good fastness properties.

The coupling components used in the manuv facture of my new dyestuffs have been described in British Patent 426,403. The invention is illustrated by the following examples, without being limited thereto:

Example 1.-2 grams of the arylamide from'3- 10;

hydroxydiphenylene-oxide-Z-carboxylic acid and l-amino-Z-methoxy 5 4 chlorobenzene are dissolved in the usual manner in a mixture from alcohol and caustic soda, and the solution is poured into one litre of water containing 10 cos.

of aqueous caustic soda lye of 38 B. strength and 10 cos. of Turkey red oil. In this solution 50 grams of cotton yarn are impregnated for /2 hour, squeezed and developed for half an hour in a developing bath prepared in the usual manner from an equimolecular quantity of diazotized 1- amino-2-methyl 4 nitrobenzene. The cotton yarn is then rinsed, soaped in a boiling bath, again rinsed and dried. A dark brown is thus obtained; the dyestuff corresponds to the follow- 5 ing formula:

l IYT==N No;

80, on (JO-NHOOI o l OCH:

In an analogous manner the impregnated yarn yields withdiazotized:

l-amino-2,5-dichlorobenzene a yellowish brown. l-arnino-z-nitroi-chlorobenzene a dark brown. 0 l-amino-2-methoxy-4-nitrobenzene Do.

l-aminc-4-nitrobenzene l-aminc-Z-methyl-fi-nitrobenzen a yellowish dark brown, 4-aminodipheny1amine a reddish brown. 4-amino-2-methy1-3-methyl-l,1'-azobena yellowish dark brown.

zene. 1-amino-2-chloro-5methoxy-4 benzoyl- Do.

aminobenzene.

The 3-hydroxydiphenyleneoxide-2-carboiwlic acid-anilide yields by coupling with diazotized:

l-amino-El-chlorobenzene a yellowish brown. 1-amino-2,5-dichlorobenzene a dark brown. 1-amino-2-methoxy-5-ch1orobenzenea blackish brown. 1-amino-2-methoxy-i-benzoylamino 5 Do.

methylbenzene. l-amino-2-methoxy-4-benzoy1amino 5 Do.

methoxybenzene. I l-amino-2-methyl-4-chlorobenzene a brown. l-amino-2-methyl-3-ehlorobenzene Do. l-amino-Z-methyl-fichlorobenzene Do. 1-amino-2-methoxybenzene 5 sulfodi- Do.

ethylamlde. l-amino-Z-chloro--benzoylamino 5 Do.

methoxybenzene. l-amino-2-methyl-5-benzoylamino 4 Do.

methylbenzene. i-amino-3-methoxydipheny1amine a reddish brown. l-aminoanthraquinone a reddish blackish brown.

a reddish brown.

4-aminodiphenylamine 1., a reddish brown.

1 amino 4 benzoylaniino 2 chloro-5- Do.

methoxybenzene.

2,5-diehloroaniline a reddish dark brown.

the dyestufi corresponds to the following formula:

011 ll CH:

0 (JO-NH CH1 l-amino-2-methyl-fi-chlorobenzene a yellowish dark brown.

l-amino-2,4- dimethyl 5 benzoylaminoa yellowish brown.

benzene.

domino-2,3-dimethyl-l,lazobenzene. a dark brown.

4-an1ino-2,4-dimethyl- 2- nitro -& metha blackish brown.

oxy-l,l-azobenzene.

y The 3 hydroxydiphenyleneoxide-2-carboxylic acid-2',6'-dimethylanilide yields with diazotized:

1-amino-2-methyl-4-ch1orobenzene a yellowish brown. 1-amino-2-chloro-5-w-triiluoro methyl- Do.

benzene 1-amino-2-methoxy-5-chlorobenzene a reddish blackish brown. Lemme-2,4 dimethyl 5 benzoylaminoa khaki.

benzene. 4-amino-2,3- dimethyll,1-az0benzene a reddish brown. l-aminoanthraquinone a yellowish black brown.

The 3 hydroxydiphenyleneoxide-2-carboxylic acid-2',5-dimethylanilide yields by coupling with diazotized:

2,5-dichloroaniline The 3 hydroxydiphenyleneoxide-2-carboxylic acid-3'5-dimethylanilide yields by coupling with diazotized:

2,5-dichloroaniline a yellowish dark brown.

The 3 hydroxydiphenyleneoxide-2-carboxylic acid-2'-anisidide yields by coupling with diazotized:

1-amino-2,5-dieh1or0benzene a yellowish dark brown. l-smino-2-n1ethoxy-5-suliodiethylamide. Do.

l-amino-2-methyl-4-chlorobenzene l-amino-Z-methyl-5-chlorobenzene a deep brown.

a yellowish brown.

l-amino-5 benzoylamino-2,4 dimethyl- Do.

benzene. 1-amino-2-chl0ro-5-m-trlfluoromethylben- Do.

zene. l-amino 4 benzoylalnino -2- chloro -.5 a reddish brown.

Inethoxybenzene. l-amino--benzoylamino 2-1nethoxy- 5 a blackish brown.

methylbenzene. l-aminoanthraquinone Do. 4-arnino-3 methyl 2 methyl 1,lazo- D0.

benzene. 2-aminodiphenylsuiione a greenish blackish brown. 4 chloro-2-an1inodiphenylether" ayellowish dark brown.

4-amino-2,5-dimethoxy-4 nitro-l, a reddish bluish black.

benzene.

The 3 hydroxydiphenyleneoxide-2-ca.1tboxylic acid-2'-phenetidide yields by coupling with diazotized:

2,5-dichl0roaniline a yellowish brown. 1-methyl-2-amino-5-nitrobenzene a' dark brown.

'acid-3',5'-dimethoxyanilide 1-methoxy-2-amino-4-nitrobenzene a khaki brown.

2-aminodiphenylsulfone an olive brown.

1 chloro 2 amino 4 methoxy an orange brown.

benzoylaminobenzene.

The 3 hydroxydiphenyleneoxide-2-carboxylic acid-4-anisidide yields by coupling with diazo- 5 tized:

l-amino-2,5-dichlorobenzene a dark brown.

The 3 hydroxydiphenyleneoxide-2carboxylic acid-2-chloroanilide yields by coupling with m diazotized:

2,5-diehloroaniline a brown.

The 3 hydroxydiphenyleneoxide-2-carboxylic acid-3-chloroanilide yields by coupling with diazotized: 15

l-amino-3-chlorobenzene a khaki. 2,5-dichloroaniline e a reddish dark brown. 1-amino-2-methyl-5-nitrobenzene akheki olive. l-amino-2-methyl-5- chlorobenzene. a grey olive. 1-amino-2-1nethyl-B-chlorobenzene a reddish brown. l-amino-Z-chlorofi-w-trifiuoromethyla brownish olive.

benzene.

The 3 hydroxydiphenyleneoxide-Z-carboxylic acid-4-chloroaniline yields by coupling with diazotized:

2,5-dichloroeniline a brown.

The 3 hydroxydiphenyleneoxide-2-carboxylic acid-2,5-dichloroanilide yields by coupling with diazotized:

2,5-dichloroaniline a dark brown.

The 3 hydroxydiphenyleneoxide-Z-carboxylic acid-3,5-dichloroanilide yields by coupling with diazotized: 4

2,5-dichloroanillne a brown. 35

The 3 hydroxydiphenyleneoxide-Z-carboxylic acid-3-nitroanilide yields by coupling with diazotized:

2,5-dichloroaniline a yellowish brown.

The 3 -hydroxydiphenyleneoxide-Z-earboxylic 0 acid-2-methyl-4-anisidide yields by coupling with diazotized:

a reddish dark brown. a dark brown.

l-amino-Z-methyi-5-chlorobenzene o. l fmino-Z-ehloro-5w-triiluoromethyla yellowish dark brown. 5

enzene. 2-amin0diphenylenesulione a greenish grey. l-amino-2emethoxy-S-chlorobenzene. a reddish blackish brown. l-amino -5- benzoylamino 2,4 dirnethyla reddishv brown.

benzene. 1 amino 4 benzoylamino-2-ehloro-5- a reddish deep brown.

methoxybenzene. 0 4 amino 2,5 dimethoxy-4-nitro l,la black.

azobenzene.

The 3 hydroxydiphenyleneoxide-2-carboxylic acid-3-methyl-4'-anisidide yields by coupling with diazotized:

Z-chloroaniline a reddish yellow brown. 3-chloroaniline Do. 2,5-dichloroaniline a yellowish dark brown. 1- amino -2,4- dimethyl 5 -benzoyl a yellowish brown.

nobenzene. l amino-2 -chloro-5 -methoxy- 4 -bena reddish brown.

zoylaminobenzene. 4-aminodiphenylan1ine e Do. 4-an1ino-4-methoxydiphenylamin Do. o-amino-azo-toluene a reddish dark brown. in-ainino-azo-toluene Do.

The 3 hydroxydiphenyleneoxide-Z-carboxy1ic acid-5-methyl-2'-anisidide yields by coupling with diazotized:

2,5-dichloroaniline a yellowish brown.

The 3 hydroxydiphenyleneoxide-2-carboxylic yields by coupling with diazotized:

' with diazotized:

l-amino-2-methoxy-5-chlorobenzenean olive grey.

l-amino-2-methyl-4-ch1orobenzene an olive brown.

l-amino-2-nitro-4-methylbenzene a blackish brown.

4-amino-2,4-di1nethyl 2- nitro 5 meth- Do.

oxy-l,l-azobenzene. V

4-a1nino-2,5-dimethoxy 4- nitro 1,1 a black.

azobenzene.

m-amino-azo-toluene a blackish brown.

o-aminoazo-toluene a yellowish dark brown. l-amino-2-methyl-3-chlorobenz a reddish brown. 1-a1'nlno-2-rnethyl-5-chlorobenzene- D0.

l-amino-2,4- dimethyl 5 benzoyla oa khaki.

benzene. l-aminoi-benzoylamino -2 -chloro 5 a reddish brown.

methoxybenzene. l-amino-2-methoxy-5-nitrobenzene a blackish brown.

The 3 hydroxydiphenyleneoxid-Z-carboxylic acid-2',5-diethoxyanilide yields by coupling with diazotized:

2,5-dich1oroaniline a yellowish brown.

The 3 hydroxydiphenyleneoxide-2-carboxylic acid-224'-dimethoxyanilide yields by coupling with diazotized:

2,5-dichloroaniline Q a yellowish brown.

The 3 hydroxydiphenyleneoxide-2-carboxylic acid-2,5'-dimethoxyani1ide yields by coupling l-amino-2-Inethyl-3-chlorobenzene a reddish brown. l-amino-2-Inethyl-5-nitrobenzene-- a dark brown. l-amino-2-n1ethoxy-5-chlorobenzene. Do. l-amino-Z-methoxy-5-sulfodiethylamide Do. 2-aminodiphenylsulfone l. Do. l-amino-2,5-dichlorobenzene a reddish brown. 4-amino-2-methyl-5-Inethoxy-2-ni 0- Do.

4-1nethyl-1,l-azobenzene. l-aminci-benzoylamino-Z-methoxya blackish brown. 5-methylbenzene. V 1-amino-2-chloro -5-wtrifluoromethyl- Do.

benzene.

4-amino-2-methyl-3-rnethyl-l,l-azobena yellowish blackish brown.

l-methoxy-Z-aminol-nitrobenzene a grey. 2,5-diethoxy-l-amino-4-benzoylaminoa corinth.

benzene. 1,3-dimethyl-4-an1ino-6-benzoylaminoa khaki.

benzene. 1-n1ethyl-2-methyl-1,1-azobenzene. a blackish brown.

The 3 hydroxydiphenyleneoxide-2-carboxylic acid-2-methoxy-5-chloroanilide yields by coupling with diazotized:

2,5-dichl0roaniline a dark brown.

l-amino-2-nitro-4-chlo1obenzene a reddish dark brown.

1-methyl-2-amino-5-nitrobenzene. a blackish brown.

2-aminodiphenylsulfone an olive brown.

l-amino-2-chloro-5-w-tri-fiuor01nethyla yellowish dark brown.

benzene.

l-chloro- 2-amino-i-methoxy-S-benzoyla reddish brown.

aminobenzene.

l-aminoanthraquinone a dark brown.

2-n1ethyl-1,1-azobenzene 7 Do. 7

The 3 hydroxydiphenyleneoxide2-carboxylic acid-2'-methoxy-5-nitroanilide yields by coupling with diazotized: 2,5-dichloroaniline a dark brown.

The 3 hydroxydiphenyleneoxide-2-carboxylic acid-2 ,4 -dimethoxy-5' -chloroanilide yields by coupling with diazotized:

l-amino-2-methy1-4-nitrobenzene a blackish brown. 1-amino-2-nitrobenzene a greylsh green.

4-chloro-2-amino-dipheny1ether ayellowish blackish brown 1-amino-4-benzoylamino-2-chloro-5-metha reddish brown.

oxybenzene.

4-amino-3-methyl-2-methyl-1;l-azoben a blackish brown.

zene.

The 3 hydroxydiphenyleneoxide-2-carboxylic acid-2 ,5 -dimethoxy-l -chloroanilide yields by coupling with diazotized:

a violet black.

dianisidine 2-am nocarbazole an orange brown. 2-81I11I10dlph6l116ll60 a yellowish brown. 3-aminodipheny1enefsulfid l D0.

The 3 hydroxydiphenyleneoxide-2-carboxylic acid-2-sulfodiethylamino-4'-chloroanilide yields by coupling with diazotized:

2,5-dichloroaniline a brown.

The 2 methyl -(3 hydroxy-2-carbonylaminodiphenyleneoxide)-benzothiazole yields by coupling with diazotized:

l-amino 2 chloro-S-w-trifluoromethyla yellowish brown.

benzene.

The 3 hydroxydiphenyleneoxide-2-carboxylic acid-a-naphthylamide yields by coupling with diazotized:

l amino-3-benzoylamino-4,6-dimethyl a brown.

benzene.

Z-aminodiphenylsulfone 2-amino-4-chlorodiphenylether.

l w trifiuorornethyl 4 chloro-3-am1 obenzene.

1-amino-i-benzcylamino-2-chloro -5 a reddish brown.

methoxybenzene.

. a greenish grey. a greylsh brown. an olive green.

Example Z.33 grams of 3-hydroxydiphenyleneoxide-Z-carboxylic acid-2'-toluidide are dissolved in water with the addition of caustic soda, and after the addition of sodium acetate a diazo solution prepared from 13.8 grams of o-nitraniline is introduced. The blackish-brown dyestuff formed is filtered with suction, washed and dried. The dyestuff has the following formula:

\ i o ONH l CH:

The dyestuff from diazotized Z-nitraniline and S-hydroxydiphenyleneoxide 2 carboxylic acid- 4'-chloroanilide, coupled in aqueous pyridine, possesses similar properties.

Example 3.-2 grams of the arylamide from 3- hydroxydiphenylenesulfide-2-carboxylic acid and l-amino-2-methoxy 4 chlorobenzene are dissolved by heating with 8 cos. of alcohol, 4; cos. of water and 1 cc. of aqueous caustic soda lye of 38 Be. The solution thus obtained is poured into one litre of water containing 10 cos. of

' aqueous caustic soda solution of 38 Be. strength.

Inthis bath 50 grams of cotton yarn are impregnated for hour, squeezed, and developed in the usual manner by introducing for hour into a diazo solution prepared from l-amino-Z-nitrol-chlorobenzene. A yellowish blackish brown is thus obtained. The dyestufi corresponds to the following formula:

In an analogousmannerthe .same coupling component yields withgdiazotized:

3-ch1oroaniline 2-nitroaniline a reddish brown.

l-amino-Z-nitro-4-methyl-benzene Do. 1-an1ino-2-methyl-3-chloro-benzene Do. Q-aminodiphenylenesulione Do. 1-amino-2- chloro 5 w trifluoromethyl- Do.

benzene. l-aminoanthraquinone Do. 3-nitroaniline a reddish blackish brown.

2. blackish brown.

a greenish black.

. a dark yellowish brown. a bluish black.

a yellowish dark brown. a violet brown.

4-nitroaniline l 1-amino-2-methyl-4-nitrobenz l-an1ino-2-1nethyl-5-nitrobenzene l-arnino-2-methoxy-4-nitrobenzen 1-amino-2-methyl-5-chlorobenzene l-a1nino-2-chloro-4-benzoyl amino 5 niethoxybenzene. 4-arnino-2-rnethyl-3-methyl-l,1 azoa brownish black.

benzene. 4-amino-3-Inethyl-2-methyl -1,1 azo- Do.

benzene.

The 3-hydroxydiphenylenesulfide-2-carboxylic acid-anilide yields by coupling with diazotized:

i-en1ino-2,5-dichlorobenzene a violet brown. 1-amino-2-methyl-5-nitrobenzene Do.

a reddish dark brown.

1-arnino-2-methyl-3-chlorobenzene 1 amino- 2 rnethoxybenzene -5 sulfo diethylamide. 1-an1ino-2-methyl-5-ehlorobenzene a reddish black. 1-arnino-2-rnethoxy-5 chlorobenzene a greenlsh black. 4 amino 3 methyl 2 methyl 1,1'- Do.

azobenzene. 1 amino 2 chloro 4 benzoylarnino .5- a violet dark brown.

methoxybenzene.

1 amino 2 Inethyl-5-benzoyla1nino -4- a greenish dark brown.

methylbenzene.

The 3-hydroxydiphenylenesulfide-2-carboxylic acid-2'-t0luidide yields by coupling with diazotized:

The 3-hydroxydiphenylenesulfide-Z-carboxylic acid-4-toluidide yields by coupling with diazotized:

3-nitraniline a reddish dark brown. 1-methoxy-2-aminobenzen -4-suliodi- Do ethylemide. l-methyl-2-arnino5-chl0robenzene a dark reddish brown.

1-rnctl10xy-2-amino-4-chlorobenzene a greenish black.

2,4-dirnethyl-2-nitro-5-methoxy-4-a1ni- Do.

no-1,1-azobenzene.

4-amino3 -methyl -2 methyl 1.1-azoa blackish brown.

benzene.

The 3-hydroxydiphenylenesulfide-2-carboxylic acid-2'-anisidide yields by coupling with diazotized:

l-ominc-2,5-diehlorobenzene l-amino-2-chloro-4-benzoylamino-5- methoxybenzene.

l-an1ino3-nitrobenzene 1-amino-2-methyl-5-nitrobenzene.. l-ami methyl-Iichlorobenzene. l-amino methyl-5-ehlorobenzene. l-amino methyl-4-nitrobenzene. l-amino- -nitro-4-methylbenzene a reddish blackish brown.

a blackish brown.

Do. a reddish dark brown.

a greenish black. a reddish brown.

l-arnino-2-rnethoxybenzene -5 sulfodi- Do.

ethylamide. 2-aminodiphenylsulf0ne Do.

a violet dark brown. 3 violet brown. a dark brown.

l-nmino-2-n1ethoxy-5-nitrobenzene 1-am1no-2-Inethoxy-5-chlorobenzene 1 amino 2 chloro 5 w trifluoromethylbenzene. 2-aminocarbazole Do. 2-arninodiphenyleneoxide- Do. B-aminodiphenylenesulfide Do. 4-amino-2,5 dimethoxy-i -nitro-l,1'- a black ezobenzene. 4-amino-2-methyl-5-methoxy-2-nitro-4- Do.

methyl-l,l-azobenzene. 4-arnino-2-methyl-3-methyl-l,1-azoa brownish black.

benzene. dianisidine a bluish black.

The 3-hydroxydiphenylenesulfide-2-carboxylic acid-4'-anisidide yields by coupling with diazotized:

3-nitraniline a reddish dark brown. 1,3-dirnethyl-4-amino -5 benzoylamino- Do.

benzene. 1-methoxy-2-amino-4-ehlorobenzene a corinth.

a yellowish dark brown.

a violet brown.

l-amino-2-nitr0benzene l-amino-2,5-diehlorobenze 1-amino-2-nitro-4-methylben Do.

l-a1nino-2-inethoxy-5-chlorobenzcn Do.

l-amino-2-n1ethyl-4-chlorobenzene a reddish dark brown.

1-amino-2-n1ethyl-4-nitrobenzene.. a greenish black.

l-arnino-Z-methyl-5-nitrobenzene a reddish blackish brown.

1 amino 2 chloro 5 w trifluoro Do.

methylbenzene.

l-amino-2-1nethoxy-B-nitrobenzene l-amino 2rnethoxy4-nitrobenzene 1 amino 2 methoxybenzene 5 sulrodiethylamidc.

1 amino 2 methyl 5 benzoylamino- 4-methylbenzene.

1 amino 2 chloro 4 benzoylamino- 5-1nethoxybenzene.

4 amino 2,5 dimethoxy 4 nitrol, l-azobenzene.

4 amino 2 methyl 5 methoxy 2 nitro-4-n1ethyl-1,l-nzobenzene.

a blackish brown. a blackish violet. a blackish reddish brown.

a dark brown.

a greenish bluish black.

a reddish black.

The 3-hydroxydiphenylenesulfide-2-carboxylic acid-4-phenetidide yields by coupling with diazotized:

1 amino 2 chloro 5 w trifluoroa blackish brown.

methylbenzene.

The 3-hydroxydiphenylenesulfide-2-carboxylic acid-2'-nitrani1ide yields by coupling with diazotized:

l-eniino-ll-chlorobenzene a brown.

The 3-hydroxydiphenylenesulfide-2-carboxylic acid-3-nitranilide yields by.coupling with diazotized:

a reddish brown.

a reddish blackish brown. an olive dark brown.

a greenish black.

The 3-hydroxydiphenylenesulfide-2-carboxylic acid 4 chloroanilide yields by coupling with diazotized:

l-amino-Z,5-dichlor0benzene a blackish brown.

The 3-hydroxydiphenylenesulfide-2-carboxylic aeid-3',4'-dichloroanilide yields by coupling with diazotized:

l-amine-2,5-diehlorobenzene a dark brown.

The 3-hydroxydiphenylenesulfide-2-carboxylic acid-3'5-dichloroanilide yields by coupling with diazotized:

2,5-diehloroaniline.. a dark brown.

The 3-hydroxydiphenylenesulfide-2-carboxylic acid-2'-methyl-4'-chloroanilide yields by coupling with diazotized:

l-aznino-Z,o-dichlorobenzene a blackish brown.

The 3-hydroxydiphenylenesulfide-2-carboxylic acid-2'-methyl-4-methoxyanilide yields by coupling with diazotized:

1-amino-2-nitrobenzene a blackish brown. i-annno-2-n1etbyl-3-chlorobenzene Do 1-mnino-2,5-diehlorobenzene a. violet blackish brown. 1-amino-2-1nethyl-4-chlorobenzene Do. 1-an1ino-2-methoxy-5-chlorobenzene. Do. 1-amino2-methoxy-5-nitrobenzene Do. 1 amino 2 chloro 4 benzoylamino 5 Do.

methoxybenzene.

4 amino 2,5 dimethoxy -4 -nitro-l,1- a greenish black.

azobenzene.

The 3-hydroxydiphenylenesulfide-2-carboxylic acid-3-methyl-4'-methoxyanilide yields by coupling with diazotized:

B-chloroaniline a reddish dark brown. 3-nitroaniline Do.

4-nitroaniline. Do. 2-nitroaniline a blackish brown. l-methyl-Z-amino a violet blackish brown.

l-amino-2-methyl-4-ch 1 amino 2 chloro-S-w -trifluorome ylbenzene.

the dyestufi corresponds to the following formula:

D o a yellowish blackish brown.

OCH;

1-amin0-2,5-dichlorobenzene a dark brown.

The 3-hydroxydiphenylenesulfide-Z-carboxylic acid-3,4'-dimethylanilide yields by coupling with diazotized:

2,5-dichloroaniline a blackish brown.

l-amino-2-methyl-5-chlorobenzene l-amino-2-chloro-5-w-triiluoromethylbenzene.

1-an1ino-2,4-dimethy1-fi-benzoylaininoa yellowish dark brown.

benzene.

4-amino-2A -dimetl1yl-2-nitr0 5- metha black. 0xy-1,1-azobenzene.

o. a yellowish blackish brown.

The 3-hydroxydiphenylenesulfide-Z-carb0xylic acid-2',4-dimeth0Xyani1ide yields by coupling with diazotized:

l-rnethyl-B-nitro-4-aminobenzene... a blackish brown.

1,3-dimethyl-4-amino-6-benzoylaininoa reddish dark brown.

benzene.

4-amino-2,3-dimethyl-1,1-azcbenzene..- a black.

The 3-hydroxydiphenylenesulfide-2-carboxylic acid-2'5-dimethcxyanilide yields by coupling with diazotized:

l-amino-2-chlorobenzene 1-- a reddish brown. l-amino-2-methyl-4-chlorobenzen Do. 1-amino-2,fi-dichlorobenzene a violet dark brown.

a reddish dark brown.

Do. a reddish black. a yellowish dark brown.

a reddish dark brown.

l-amino-il-nitrobenzene.

l-amino-2-methyl-3-chlorob l-amino-2-methyl-5-n1trobenzene 1-amino-2-methyl-4-nitrobenzene 1-amino-2-methyl-5-benzoylam1no 4 methylbenzene.

l-amino -2- chloro 5-w triflucromethylbenzene.

1 amino 2 chloro 4 benzoylamlno- S-methoxybenzene.

The 3-hydroxydiphenylenesulfide-2-carboxylic acid-3',5'-dimethoxyanilide yields by coupling with diazotized:

l-amino-2-methyl-4-chlorobenzene a brown.

The 3-hydroxydiphenylenesulfide-2-carboxy1ic a dark brown.

acid-3',6 dimethoxyi'echloroanilide yields by coupling with diazotized:

1-amino-3-chl0rcbenzene a reddi h dark brown.

l-amino-z,5-dichlorobenzene Do 1-amino-Z-methyl-3-chlorobenzene Do. l-amino-2-1nethyl-4-chlorobenzene Do. 1 amino 2 chloro 5 w trifluoro- De.

methylbenzene. l-amino-2-methyl-fi-chlcrobenzene a black a vuget dark brown.

l-amino-El-nitrobenzene l-amino-2-methoxy-5-chlorobenzene 0. l amino 2 methoxyb enzene 5 sulfo- Do.

diethylamide. l-amino-2-methoxy-5-nitrobenzene Do. l-amino-Z-methyl-G-nittobenzene a corinth l-arnino-2-chloro-4-benzoylamino 5 areddish blackish brown.

methoxybenzene. 1

The 3-hydroxydipheny1enesulfide-2-carb0xy1ic acid-2,4-dimethoxy-5-ch1oroanilide yields by coupling with cliazotized:

l-amino-2,5-dichlorobenzene a blackish brown.

The 3-hydroxydipheny1enesulfide-2-carboxylic acid-a-naphthalide yields by coupling with diazotized:

l-amino-2-chlprobenzene a reddish dark brown. l-amrno-Z,5-dichlorobenzene-. a blackish brown. l-annno-2-methyl-5-chlorobenz Do. l-amino-2-chloro-5-w-trifluoro me Do.

benzene. 1-amino.-2,4-dimethyl- 5 benzoylamino- Do.

benzene. 4-aminediphenylamine 4',1 azo 2- D0.

methyl-4-amino-5-methoxybenzene. l-amino-3-nitrobenzene a violet dark brown. l-ammo-2-methyl-3-chlorobenzene D0. l-amino-2-methyl-4-chlorobenzene Do. 1-amino-2-methyl-5-nitrobenzene.-- Do. l-amino-2-methoxy-5-chl0robenzene Do. l-amino-2-n ethyl-4-nitrobenzene. a black. lam no-2-mtro-4-methylbenzen a bluish grey. l-am no-2-methoxy4-nitrobenzene a reddish bluish black. l-ainuio-2-methoxybenzene 5 sulfoa violet grey.

dlethylamide. l-am no-Z-methoxy-5-nitrobenzene-; a blackish violet. 1-am1no-2-methoxy-4-benzoylamino 5 a reddish dark blue.

methoxybenzene. 4-am1no 2 methyl-3'-methyl-1,1'-azoa brownish black.

benzene. 4 amino 3-methyl-2-methyl-1,1-azoa greenish black.

benzene. 4 amino 2,5-dimethoxy-4-nitro-1,1- Do.

azobenzene.

The 2-methy1-6-(3'-hydroxy-2-carboylaminodiphenylene-sulfide') -benzothiazo1e yields by coupling with diazotized:

1 amino -2- chlorc-li-w-trifluoromethyle blackish brown.

benzene.

The 1- (3-hydroxy 2 carboylaminodiphenylene-sulfide) carbazole yields by coupling with diazotized:

l-amino-Zmitrobenzene a grey. 1-amino-2-methyl-5-nitrobenzene- D0. 1-amino-2-methoxy-5-nitrobenzene Do 1-amino-2,5-dichlorobenzene a yellowish dark brown.

l-ammo 2 ch1oro-5w -trifluoromethyla yellowish blackish brown.

benzene.

l-amino-2-methyl-4-n.itrobenzene a black.

1-amino-Z-methoxyl-nitrobenzenea bluish black. 4-chloro-2-am1no-diphenylether a blackish brown. 2-amino-diphenylenesulione Do.

The arylide from 2 mols of 3-hydroxydiphenylenesulfide-Z-carboxylic acid and 1 mol of dianisidine yields by coupling with diazotized:

1-amino-2,5-dichlorobenzene a dark brown.

The 6 ethoxy 2 -(3 hydroxy-2'-carbonylaminodiphenylenesulfide) -benzothiazole yields by coupling with diazotized:

l-emino-2,5-dichlorobenzene a brown.

Example 4.34.9 grams of B-hydroxydiphenylenesulfide-2-carboxylic acid-2-anisidide are dissolved in water with the aid of aqueous caustic soda lye. Then sodium acetate is added, and after this a diazo solution prepared from 15.2 grams of 1-amino-2-nitro-4-methylbenzene is introduced. The blackish brown azodyestufl which separates and corresponding to the follow ing formula:

Gil

is sucked oif, washed and dried.

This is a continuation-in-part of my application for Letters Patent Ser. No. 690,950, filed September 25, 1933.

I claim:

1. Waterinsoluble azodyestuffs of the general formula:

NraN-l R wherein X stands for a sulfur or an oxygen atom, R and R for aromatic radicals and n stands for one of the numbers one and two, yielding, when produced on the fibre, generally brown to blackish brown to black shades of good fastness properties.

2. Waterinsoluble azodyestufis ofthe general formula:

wherein X stands for a sulfur or an oxygen atom,

R'stands for the radical of-a diazo compound suitable for producing azodyestuffs and R stands for a radical of the benzeneseries, yielding, when produced on the fibre, generally brown to blackish brown to black shades of good fastness properties.

3. waterinsoluble azodyestufis of thegeneral formula:

wherein X stands for a sulfur or an oxygen atom and R and R? stand for radicalsof the benzene series, yielding, when produced on the fibre, generally brown to blackish brown to black shades of good fastness properties.

4. The dyestufi of the following formula:

yielding, when produced on the fibre, reddish dark brown shades of good fastness properties. 30

6. The dyestufi'of the following formula:

yielding, when-produced on the fibre, yellowish blackish brown shades of good fastness properties.

7. Fibre dyed with' adyestufl' as claimed in claim'l.

8. Fibre dyed with a dyestufi. as claimed in claim 2.

9. Fibre dyed with a dyestuif as'claimed in claim 3.

10; Fibre'dyed withthedyestufl as claimed in claim 4.

11. Fibre dyed with the dyestufiasclaimed in claim 5.

12. Fibre dyed with the dyestufi as claimedln claim 6.

FRIEDRICH MUTH. 

